EP0064205A1 - Crystalline aluminosilicate, process for producing it and its use in converting methanol and/or dimethyl ether into hydrocarbons - Google Patents

Crystalline aluminosilicate, process for producing it and its use in converting methanol and/or dimethyl ether into hydrocarbons Download PDF

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EP0064205A1
EP0064205A1 EP82103256A EP82103256A EP0064205A1 EP 0064205 A1 EP0064205 A1 EP 0064205A1 EP 82103256 A EP82103256 A EP 82103256A EP 82103256 A EP82103256 A EP 82103256A EP 0064205 A1 EP0064205 A1 EP 0064205A1
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crystalline aluminosilicate
methanol
catalyst
zeolite
hydrocarbons
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EP0064205B1 (en
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Lothar Dr. Puppe
Jürgen Dr. Weisser
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Bayer AG
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7038MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/46Other types characterised by their X-ray diffraction pattern and their defined composition
    • C01B39/48Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0425Catalysts; their physical properties
    • C07C1/043Catalysts; their physical properties characterised by the composition
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00Catalysts comprising molecular sieves
    • C07C2529/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02BINTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B1/00Engines characterised by fuel-air mixture compression
    • F02B1/02Engines characterised by fuel-air mixture compression with positive ignition
    • F02B1/04Engines characterised by fuel-air mixture compression with positive ignition with fuel-air mixture admission into cylinder

Definitions

  • the invention relates to a new zeolite-like material, hereinafter referred to as PSH-3, and a method for producing the same and its use as a catalyst in the production of hydrocarbons from methanol and / or dimethyl ether.
  • Zeolites are water-containing framework silicates. They can be described as a rigid three-dimensional framework of SiO 4 - and A10 4 tetrahedra describe that are linked through common oxygen atoms. The charge of the AlO 4 tetrahedron is negative and is balanced, for example, by alkali or alkaline earth metalation. The cavities of the crystalline aluminosilicate are filled with water molecules that can be removed without the framework breaking down.
  • the present invention relates to a new zeolite material, that is to say a crystalline aluminosilicate, with a composition corresponding to the formula (in molar ratios of the oxides): where M is a cation of valence n and with a powder X-ray diagram essentially as indicated in Table 1.
  • the crystalline aluminosilicate according to the invention can be obtained from a synthesis mixture which contains a silica, an Al compound, alkali and hexamethyleneimine.
  • the zeolite PSH-3 proves to be different from all known natural and synthetic zeolites.
  • the zeolite PSH-3 according to the invention has the following oxidic composition and has a Polver X-ray diagram, as in the we substantial is listed in Table I.
  • the SiO 2 / Al 2 O 3 ratio is preferably 30-100.
  • the zeolite PSH-3 in the preferably synthesized form has the following composition: R is an organic nitrogen-containing cation derived from hexamethyleneimine.
  • Hexamethyleneimine is a seven-membered heterocycle with one nitrogen atom.
  • the synthesis mixture is preferably kept in the following ranges:
  • the crystalline aluminosilicate zeolite PSH-3 has the following characteristic lines in the X-ray diagram, which are listed in Table I.
  • the values were determined using the K ⁇ radiation of the copper.
  • the original cations of the zeolite can already be replaced by ion exchange with other cations known techniques to be replaced.
  • the exchange is preferably carried out after calcining the zeolite.
  • the reaction time at a temperature of 80 to 180 ° C, about 12 to 144 hours, preferably 110 to 150 ° C for 24 to 96 hours.
  • the crystalline product obtained is separated from the mother liquor, washed with water to a pH of 8-10 in the running water and dried at 120.degree.
  • the Zeoltih PSH-3 is used as an adsorbent or preferably as a catalyst, the org. Connections and water from the cavities. This is done by heating to 300 to 600 ° C in an atmosphere such as air, nitrogen, ammonia, etc. within 1 to 24 hours.
  • zeolites as a catalyst.
  • a modification is necessary, as can be done by already known techniques of ion exchange.
  • the H-form of the zeolite is obtained either by the action of dilute acids or by exchange with ammonium salts and subsequent calcination.
  • the zeolite PSH-3 is preferably used in the dehydrated H form. It is also advantageous if a mixture of the H form with a metal-exchanged form, for example the Mg, Mn, Ba and / or rare earth form, is processed to form a catalyst.
  • a metal-exchanged form for example the Mg, Mn, Ba and / or rare earth form
  • Zeolite PSH-3 can be processed into catalysts in a variety of particle sizes.
  • the particles can be used in the form of a powder, granules or as shaped bodies.
  • zeolite PSH-3 described above is processed with inert materials and / or binders to industrially useful catalysts.
  • the inert materials or binders, clays, clays, bentonites, smectites, naturally occurring or synthetically produced metal for example aluminum oxide, silicon dioxide, titanium dioxide, zirconium dioxide, thorium oxide, tin oxide, zinc oxide, magnesium oxide and / or beryllium oxide.
  • the relative proportions of the zeolite component can be varied within wide limits with regard to the support material used; namely in the range from 1 to 99% and preferably 10 to 80% by weight, based on the dry catalyst mass.
  • the PSH-3 zeolite described above is suitable as a catalyst for the conversion of lower aliphatic alcohols and / or ethers, preferably methanol and / or dimethyl ether, into predominantly ali-. phatic unsaturated hydrocarbons with low aromatic content.
  • methanol and / or dimethyl ether on zeolites of the ZSM-5 or ZSM-11 type can be converted into water and an aromatic-rich hydrocarbon fraction.
  • the catalyst activity can be reduced such that the reaction products are predominantly aliphatic in nature are.
  • the preparation of the catalysts is complex and technically not harmless due to the toxicity of organic phosphines, phosphine oxides, phosphoric acid derivatives, etc. (US Pat. No. 3,911 Q41).
  • the inventive use of the zeolite PSH-3 as a catalyst for the conversion of methanol and / or dimethyl ether can be carried out either batchwise, semi-continuously or continuously. It is irrelevant whether the catalyst is fixed or movable.
  • the methanol insert can consist of pure methanol or of technical crude methanol containing water and oxygenate. An additional dilution of the insert with water can also be carried out.
  • This regeneration is expediently carried out by supplying an oxygen-containing atmosphere (for example air or air-nitrogen mixtures) to the catalyst at elevated temperature using known techniques.
  • the regeneration temperature should not exceed 600 ° C.
  • synthesis gas can be used directly as the feedstock to be converted, provided that the zeolite PSH-3 is coated with metals which are catalytically suitable for the methanol or Fischer-Tropsch synthesis.
  • the aluminosilicate according to the invention can thus be used in conjunction with catalysts which are suitable for the hydrogenation of carbon oxides. While the fraction of longer-chain hydrocarbons (C 5+ ) that occurs in the usual implementation of the carbon oxide hydrogenation (FISCHER- T ROPSCH synthesis with metal-containing catalysts) often shows up to over 20 to 25 C atoms in the molecule and is largely straight-chain , the application of the aluminosilicate according to the invention as a cocatalyst in the catalytic hydrogenation of carbon dioxide provides, among other product components, a Ce-hydrocarbon mixture which consists predominantly of molecules with 5 to 12 carbon atoms.
  • This chain length-limiting effect of the aluminosilicate according to the invention is associated with the formation of branched hydrocarbons and possibly further reactions leading to aromatics if the reaction is carried out appropriately, so that, for example, a hydrocarbon mixture prepared in this way is much more suitable for further processing in petrol than is the case with the usual execution of FISCHER TROPSCH synthesis resulting hydrocarbon mixture.
  • a mixture of 217 ml water glass (27% SiO 2 and 8% Na 2 O) and 316 ml water is mixed with 49.5 g hexamethyleneimine and stirred vigorously in a 2 liter steel autoclave with a stirring insert.
  • a solution of 9.22 g of Al sulfate, 23.4 g of H 2 SO 4 (conc.) And 460 ml of water is slowly poured into this mixture with stirring
  • the solid is separated from the liquid phase, washed out until the pH was 7-9 and dried at 120.degree.
  • the zeolite had the specified table in the X-ray diffraction data and after calcination at 500 ° C fol.
  • zeolite PSH-3 in the calcined form 100 g are stirred with 1000 ml of 0.5N HCl at 80 ° C. for 5 hours. The solid is separated off and washed. The exchange is repeated two more times.
  • the H form of the zeolite can be used as a catalyst for the production of hydrocarbons from methanol.
  • Example 1 The batch as in Example 1 was crystallized at 130 ° C. within 144 hours.
  • the crystalline product obtained had the same X-ray data as the zeolite PSH-3 from Example 1.
  • a mixture of 650 g of silica sol, 790 ml of water and 78 g of NaOH is mixed with 124 g of hexamethyleneimine in a 5 liter steel autoclave with a stirrer insert. This mixture slowly becomes a solution. 23 g of Al-sulfonic fa t, 58.5 g H 2 SO 4 (conc.) And 1150 ml H 2 0 woks.
  • the reaction mixture is allowed to crystallize at 150 ° C. for 5 days with stirring.
  • the crystalline solid is separated off, washed out until the pH in the effluent water was 8-9. After calcination, the zeolite had the X-ray diffraction data in Table 1.
  • the crystalline end product mainly had the X-ray data in Table 1, in addition to small amounts of quartz.
  • the crystalline end product had the following oxidic composition: 0.2 Na 2 0, A1 2 0 3 , 41 Si0 2 .
  • Examples 7 to 8 below relate to the use of the zeolite PSH-3 prepared according to Examples 1-6 as a catalyst for the conversion of methanol and / or dimethyl ether into hydrocarbons.
  • the catalyst was brought to a reaction temperature of 370 ° C. under nitrogen and then charged with gaseous methanol in an amount of 790 g per liter of catalyst per hour.
  • This example relates to the conversion of a methanol / dimethyl ether / water equilibrium mixture into predominantly aliphatic-olefinic hydrocarbons.
  • a stream of 50 ml of methanol per hour was passed in vaporized form without applying pressure at a temperature of 280 ° C. over a bed of catalyst consisting of 100 ml of precipitated and granulated aluminum oxide.
  • aluminum oxide catalyzes the conversion of methanol to dimethyl ether (see, for example, JB Senderens, Ann. Chim. Phys. 25, 509 (1912).
  • the product mixture leaving the reactor was passed through a mixture according to Examples 1 and 2 without further separation prepared and granulated with an addition of 20% Montigel according to known techniques based on zeolite PSH-3.
  • the contact load was 800 g insert per liter catalyst and hour; the transition temperature was 370 ° C.
  • the product stream leaving the reactor was composed as follows (without taking the water of reaction into account):
  • C -Share can also contain small amounts of oxygen-containing compounds.
  • D can be a the resultant dimethyl ether recycled, is calculated for the aliphatic hydrocarbons in the B enzinsiede Suite (C , P + O) a carbon selectivity of approx. 47%. This value increases to approx. 83% if C 3 and C 4 hydrocarbons are also added.
  • Carburetor fuels can also be obtained from the latter using known techniques (alkylation processes).
  • the precipitate was filtered off, washed neutral with water and dried for 4 h at 150 ° C. in vacuo (20 torr). After grinding, the mass was pressed with graphite and bentonite into cylindrical 5 x 5 mm tablets.
  • the catalyst was first filled for 14 h at 300 ° C, normal pressure and a gas load of 1000 Nl / (hx 1 catalyst) and then with carbon monoxide for 8 h at 300 ° C, normal pressure and a gas load of-1000 Nl / (hx 1 catalyst ) treated.
  • the chain length-limiting effect of the aluminosilicate according to the invention can be seen from the information in the two examples, according to which 95% by weight of the C 5+ fraction has 12 12 C atoms in the molecule.

Abstract

Die vorliegende Erfindung betrifft ein neues Zeolithmaterial mit einer Zusammensetzung (Molverhältnisse der Oxide) etwa der Formel M2/n O . Al2O3 . (20 - 150) SiO2 (M = Kation der Wertigkeit n), ein Verfahren zu dessen Herstellung unter Verwendung von Hexamethylenimin sowie die Verwendung des Zeolithmaterials als Katalysator für die Umwandlung von Methanol und/oder Dimethylether in Kohlenwasserstoffe.The present invention relates to a new zeolite material with a composition (molar ratio of oxides) approximately of the formula M2 / n O. Al2O3. (20 - 150) SiO2 (M = cation of valence n), a process for its production using hexamethyleneimine and the use of the zeolite material as a catalyst for the conversion of methanol and / or dimethyl ether into hydrocarbons.

Description

Gegenstand der Erfindung ist ein neues zeolithartiges Material, das nachfolgend als PSH-3 bezeichnet wird, sowie ein Verfahren zur Herstellung desselben und dessen Verwendung als Katalysator bei der Herstellung von Kohlen-' wasserstoffen aus Methanol und/oder Dimethylether.The invention relates to a new zeolite-like material, hereinafter referred to as PSH-3, and a method for producing the same and its use as a catalyst in the production of hydrocarbons from methanol and / or dimethyl ether.

Unter Zeolithe versteht man wasserhaltige Gerüstsilikate. Sie lassen sich als starres dreidimensionales Gitter von SiO4 - und A104-Tetraedern beschreiben, die durch gemeinsame Sauerstoffatome verknüpft sind. Die Ladung des AlO4-Tetraeders ist negativ und wird beispielsweise durch ein Alkali- bzw. Erdalkalikation ausgeglichen. Die Hohlräume des kristallinen Alumosilicate sind mit Wassermolekülen besetzt, die entfernt werden können, ohne daß das Gerüst zusammenbricht.Zeolites are water-containing framework silicates. They can be described as a rigid three-dimensional framework of SiO 4 - and A10 4 tetrahedra describe that are linked through common oxygen atoms. The charge of the AlO 4 tetrahedron is negative and is balanced, for example, by alkali or alkaline earth metalation. The cavities of the crystalline aluminosilicate are filled with water molecules that can be removed without the framework breaking down.

Es ist bekannt, organische Stickstoffverbindungen für Zeolith-Synthesen einzusetzen. Hierbei werden vor allem SiO2-reiche Zeolith-Typen erhalten. Am bekanntesten sind in letzter Zeit Zeolithe mit der Bezeichnung ZSM 5 bzw. ZSM 11 geworden, die besondere katalytische Eigenschaften aufweisen. Einen überblick der Zeolithe, die mit Hilfe organischer Kationen erhalten wurden, findet man in "Zeolite Molekular Sieves" von D.W. Breck (Wiley, Interscience 1974), Seiten 304 bis 312 und 348 bis 378.It is known to use organic nitrogen compounds for zeolite syntheses. In particular, zeolite types rich in SiO 2 are obtained. Zeolites with the designations ZSM 5 and ZSM 11 have become best known in recent times, the special catalytic properties have ten. An overview of the zeolites obtained with the aid of organic cations can be found in "Zeolite Molecular Sieves" by DW Breck (Wiley, Interscience 1974), pages 304 to 312 and 348 to 378.

Gegenstand der vorliegenden Erfindung ist ein neues Zeolithmaterial, also ein kristallines Alumosilicat, mit einer Zusammensetzung entsprechend der Formel (in Molverhältnissen der Oxide):

Figure imgb0001
wobei M ein Kation der Wertigkeit n ist und mit einem Pulver-Röntgendiagramm im wesentlichen wie in Tabelle 1 angegeben.The present invention relates to a new zeolite material, that is to say a crystalline aluminosilicate, with a composition corresponding to the formula (in molar ratios of the oxides):
Figure imgb0001
where M is a cation of valence n and with a powder X-ray diagram essentially as indicated in Table 1.

Das erfindungsgemäße kristalline Alumonosilicat kann aus einer Synthesemischung erhalten werden, die eine Kieselsäure, eine Al-Verbindung, Alkali und Hexamethylenimin enthält.The crystalline aluminosilicate according to the invention can be obtained from a synthesis mixture which contains a silica, an Al compound, alkali and hexamethyleneimine.

Der Zeolith PSH-3 erweist sich anhand von Röntgenbeugungsdaten und anderen Charakteristiken als unterschiedlich von allen bisher bekannten natürlichen und synthetischen Zeolithen.On the basis of X-ray diffraction data and other characteristics, the zeolite PSH-3 proves to be different from all known natural and synthetic zeolites.

Der erfindungsgemäße Zeolith PSH-3 hat folgende oxidische Zusammensetzung

Figure imgb0002
und besitzt ein Polver-Röntgendiagramm, wie es im wesentlichen in der Tabelle I aufgeführt wird.The zeolite PSH-3 according to the invention has the following oxidic composition
Figure imgb0002
and has a Polver X-ray diagram, as in the we substantial is listed in Table I.

Vorzugsweise beträgt das SiO2/Al2O3-Verhältnis 30-100.. Der Zeolith PSH-3 hat in der bevorzugt synthetisierten Form folgende Zusammensetzung:

Figure imgb0003
R ist ein sich vom Hexamethylenimin ableitendes organisches stickstoffhaltiges Kation.The SiO 2 / Al 2 O 3 ratio is preferably 30-100. The zeolite PSH-3 in the preferably synthesized form has the following composition:
Figure imgb0003
R is an organic nitrogen-containing cation derived from hexamethyleneimine.

Entsprechend dem Herstellungsverfahren wird ein Gemisch aus einer Mineralsäure, Na20, SiO2, Al2O3, Hexamethylenimin und Wasser gebildet, das die Zusammensetzung in Molverhältnissen von Oxiden in den folgenden Bereichen aufweist:

Figure imgb0004
wobei R = Hexamethylenimin ist.According to the production process, a mixture of a mineral acid, Na 2 O, SiO 2 , Al 2 O 3 , hexamethyleneimine and water is formed, which has the composition in molar ratios of oxides in the following ranges:
Figure imgb0004
where R = hexamethyleneimine.

Hexamethylenimin ist ein siebengliedriger Heterocyclus mit einem Stickstoffatom.Hexamethyleneimine is a seven-membered heterocycle with one nitrogen atom.

Vorzugsweise wird die Synthesemischung in folgenden Bereichen gehalten:

Figure imgb0005
The synthesis mixture is preferably kept in the following ranges:
Figure imgb0005

Der kristalline Alumosilicat-Zeolith PSH-3 hat folgende charakteristische Linien im Röntgendiagramm, die in der Tabelle I anfgeführt sind.The crystalline aluminosilicate zeolite PSH-3 has the following characteristic lines in the X-ray diagram, which are listed in Table I.

Die Werte wurden mit der K α-Strahlung des Kupfers ermittelt. Die relativen Intensitäten 100 I/I0, wobei I0 die Intensität der stärksten Linie und d der Netzebenenabstand in Å ist, wurden aus dem Schreiberdiagramm ermittelt.The values were determined using the K α radiation of the copper. The relative intensities 100 I / I 0 , where I 0 is the intensity of the strongest line and d the network plane spacing in Å, were determined from the plotter diagram.

In der Tabelle I werden die relativen Intensitäten wie folgt beschrieben.

Figure imgb0006
Figure imgb0007
Figure imgb0008
In Table I, the relative intensities are described as follows.
Figure imgb0006
Figure imgb0007
Figure imgb0008

Die Gleichgewichtsadsorptionen des kristallinen Alumosilicats PSH-3 für einige Verbindungen sind in der folgenden Tabelle II aufgeführt.

Figure imgb0009
The equilibrium adsorptions of the crystalline aluminosilicate PSH-3 for some compounds are shown in Table II below.
Figure imgb0009

Die ursprünglichen Kationen des Zeoliths können durch Ionenaustausch mit anderen Kationen nach bereits bekannten Techniken ersetzt werden. Bevorzugt erfolgt der Austausch nach dem Calcinieren des Zeoliths.The original cations of the zeolite can already be replaced by ion exchange with other cations known techniques to be replaced. The exchange is preferably carried out after calcining the zeolite.

Der krist. Zeolith wird durch Kristallisieren eines Reaktionsgemisches einer Zusammensetzung in den folgenden oxidischen Molverhältnissen erhalten:

Figure imgb0010
wobei R = Hexamethylenimin (CH2)6NH ist.The krist. Zeolite is obtained by crystallizing a reaction mixture of a composition in the following oxidic molar ratios:
Figure imgb0010
where R = hexamethyleneimine (CH 2 ) 6 NH.

Die Reaktionsdauer beträgt bei einer Temperatur von 80 bis 180°C, ca. 12 bis 144 Stunden, bevorzugt 110 bis 150°C 24 bis 96 Stunden.The reaction time at a temperature of 80 to 180 ° C, about 12 to 144 hours, preferably 110 to 150 ° C for 24 to 96 hours.

Das erhaltene kristalline Produkt wird von der Mutterlauge abgetrennt, mit Wasser auf einen pH-Wert im ablaufenden Wasser von 8 - 10 gewaschen und bei 120°C getrocknet.The crystalline product obtained is separated from the mother liquor, washed with water to a pH of 8-10 in the running water and dried at 120.degree.

Wird der Zeoltih PSH-3 als Adsorbens oder bevorzugt als Katalysator eingesetzt, so erfolgt unter Anwendung üblicher Techniken eine Entfernung der org. Verbindungen und des Wassers aus den Hohlräumen. Dies geschieht durch Erhitzen auf 300 bis 600°C in einer Atmosphäre wie Luft, Stickstoff, Ammoniak usw. innerhalb von 1 bis 24 Stunden.If the Zeoltih PSH-3 is used as an adsorbent or preferably as a catalyst, the org. Connections and water from the cavities. This is done by heating to 300 to 600 ° C in an atmosphere such as air, nitrogen, ammonia, etc. within 1 to 24 hours.

Die Ausgangsstoffe für die Herstellung des erfindungsmäßen Zeoliths sind Materialien, die die geeigneten oxidischen Verbindungen liefern. Hierfür kommen beispielsweise in Frage Na-Aluminat, Al-Sulfat, Al (OH)3, A1203, Kieselsol, SiO2-Füllstoffe, Na-Silikate, NaOH sowie Mineralsäuren wie z.B. H2SO4 und als org. Verbindung Hexamethylenimin.The starting materials for the manufacture of the Invention Moderate zeolites are materials that provide the appropriate oxidic compounds. For example, Na aluminate, Al sulfate, Al (OH) 3 , A1 2 03, silica sol, SiO 2 fillers, Na silicates, NaOH and mineral acids such as H 2 SO 4 and as org. Compound hexamethyleneimine.

Für eine weitere Verwendung der krist. Zeolithe als Katalysator ist. im allgemeinen eine Modifizierung notwendig, wie sie durch bereits bekannte Techniken des Ionenaustausches erfolgen kann. So erhält man die H-Form des Zeoliths entweder durch Einwirken von verdünnten Säuren bzw. durch Austausch mit Ammoniumsalzen und anschließender Calcinierung.For further use of the krist. Zeolites as a catalyst. generally a modification is necessary, as can be done by already known techniques of ion exchange. The H-form of the zeolite is obtained either by the action of dilute acids or by exchange with ammonium salts and subsequent calcination.

Weiterhin sind Austausche mit Ubergangsmetallionen, z.B. der Gruppen VIIa, VIIIa, Ib und IIb möglich. Zusätzliche Austausche bzw. Modifikationen mit Hauptgruppenelementen sind durchführbar.Furthermore, exchanges with transition metal ions, e.g. of groups VIIa, VIIIa, Ib and IIb possible. Additional exchanges or modifications with main group elements can be carried out.

Für die erfindungsgemäße Anwendung wird der Zeolith PSH-3 vorzugsweise in der dehydratisierten H-Form eingesetzt. Ebenso ist es vorteilhaft, wenn ein Gemisch der H-Form mit einer Metall-ausgetauschten Form, beispielsweise der Mg-, Mn-, Ba- und/oder Seltenerdform zu einem Katalysator verarbeitet wird.For the application according to the invention, the zeolite PSH-3 is preferably used in the dehydrated H form. It is also advantageous if a mixture of the H form with a metal-exchanged form, for example the Mg, Mn, Ba and / or rare earth form, is processed to form a catalyst.

Der Zeolith PSH-3 kann in einer Vielzahl von Teilchengrößenzu Katalysatoren verarbeitet werden.Zeolite PSH-3 can be processed into catalysts in a variety of particle sizes.

Je nach verfahrenstechnischer Durchführung (Flugstaubverfahren, Wirbelschichtverfahren, Wanderbettverfahren, Festbettverfahren) können die Teilchen in Form eines Pulvers, eines Granulats oder als Formkörper eingesetzt werden.Depending on the procedural implementation (fly dust process, fluidized bed process, moving bed process, Fixed bed process) the particles can be used in the form of a powder, granules or as shaped bodies.

Zur Herstellung der verschiedenen Anwendungsformen, die nach bekannten Techniken geschehen kann,.ist es u.U. erforderlich, daß man den vorstehend beschriebenen Zeolith PSH-3 mit Inertmaterialien und/oder Bindemitteln zu technisch brauchbaren Katalysatoren verarbeitet.It may be necessary to produce the various forms of use, which can be done using known techniques. required that the zeolite PSH-3 described above is processed with inert materials and / or binders to industrially useful catalysts.

Beispielsweise sind für die Herstellung technischer Katalysatoren auf Basis Zeolith PSH-3 die Inertmaterialien bzw. Bindemittel, Tone, Tonerden, Bentonite, Smectite, natürlich vorkommende oder synthetisch hergestellte Metall- . oxide, beispielsweise Aluminiumoxid, Siliciumdioxid, Titandioxid, Zirkoniumdioxid, Thoriumoxid, Zinnoxid, Zinkoxid, Magnesiumoxid und/oder Berylliumoxid geeignet.For example, for the manufacture of technical catalysts based on zeolite PSH-3, the inert materials or binders, clays, clays, bentonites, smectites, naturally occurring or synthetically produced metal. oxides, for example aluminum oxide, silicon dioxide, titanium dioxide, zirconium dioxide, thorium oxide, tin oxide, zinc oxide, magnesium oxide and / or beryllium oxide.

Die relativen Anteile der Zeolithkomponente können im Hinblick auf das verwendete Trägermaterial in weiten Bereichen variiert werden; nämlich im Bereich von 1 bis 99 % und bevorzugt 10 bis 80 Gew.-%, bezogen auf die trockene Katalysatormasse.The relative proportions of the zeolite component can be varied within wide limits with regard to the support material used; namely in the range from 1 to 99% and preferably 10 to 80% by weight, based on the dry catalyst mass.

Der vorsthend beschriebene Zeolith PSH-3 eignet sich als Katalysator für die Umwandlung von niederen aliphatischen Alkoholen und/oder Ethern, vorzugsweise Methanol und/oder Dimethylether, in überwiegend ali- . phatisch ungesättigte Kohlenwasserstoffe mit niedrigen Aromatengehalt.The PSH-3 zeolite described above is suitable as a catalyst for the conversion of lower aliphatic alcohols and / or ethers, preferably methanol and / or dimethyl ether, into predominantly ali-. phatic unsaturated hydrocarbons with low aromatic content.

Beispielsweise ist bekannt, daß sich Methanol und/oder Dimethylether an Zeolithen vom Typ ZSM-5 oder ZSM-11 .in Wasser und eine aromatenreiche KohlenwasserstoffFraktion umwandeln läßt.For example, it is known that methanol and / or dimethyl ether on zeolites of the ZSM-5 or ZSM-11 type can be converted into water and an aromatic-rich hydrocarbon fraction.

Beispielsweise ist in dpr US-PS 3 894 107 beschrieben, daß das durch Zeolith-Katalyse aus Methanol enthaltene Kohlenwasserstoffgemisch zu 40 % und mehr aus Aromaten bestehen kann. Weiterhin lehrt die US-PS 3 894 105, daß die aus Methanol erhaltenen Aromaten einen beträchtlichen Anteil an 1,2,4,5-Tetramethylbenzol(Durol) aufweisen. Bei Verwendung des aus Methanol erhaltenen Kohlenwasserstoffgemisches als Vergaserkraftstoff ist der Duolanteil in der Aromatenfraktion nachteilig:

  • Durol ist in Kohlenwasserstoffen bei Raumtemperatur schwerlöslich, und es neigt aufgrund seines hohen Schmelzpunktes (79,2°C) zum Auskristallisieren. Es ist offentsichtlich, daß dieses Auskristallisieren Störungen beim Betrieb von Verbrennungsmotoren verursachen kann, die mit aus Methanol hergestelltem Kraftstoff betrieben werden. Es hat zahlreiche Versuche gegeben, die Umwandlung von Methanol an Zeolithen so zu steuern, daß die flüssigen Reaktionsprodukte nur wenig Durol bzw. allgemein wenig Aromaten enthalten.
In d p r example, U.S. Patent No. 3,894,107 described that the hydrocarbon mixture contained by zeolite catalysis of methanol to 40% and may consist of more aromatics. Furthermore, US Pat. No. 3,894,105 teaches that the aromatics obtained from methanol contain a considerable amount of 1,2,4,5-tetramethylbenzene (Durol). If the hydrocarbon mixture obtained from methanol is used as the gasoline, the duol content in the aromatic fraction is disadvantageous:
  • Durol is sparingly soluble in hydrocarbons at room temperature and due to its high melting point (79.2 ° C) it tends to crystallize. It is obvious that this crystallization can cause disturbances in the operation of internal combustion engines which are operated with fuel made from methanol. There have been numerous attempts to control the conversion of methanol to zeolites in such a way that the liquid reaction products contain little durol or generally little aromatics.

Beispielsweise läßt sich durch Modifizieren eines ZSM-5 Zeolithkatalysators mit organischen Verbindungen des Phosphors die Katalysatoraktivität derartig herabsetzen, daß die Reaktionsprodukte vorwiegend aliphatischer Natur sind. Allerdings ist die Herstellung der Katalysatoren aufwendig und in technischer Hinsicht aufgrund der Toxizität von organischen Phosphinen, Phosphinoxiden, Phosphorsäurederivaten etc. nicht unbedenklich (US-PS 3 911 Q41).For example, by modifying a ZSM-5 zeolite catalyst with organic compounds of phosphorus, the catalyst activity can be reduced such that the reaction products are predominantly aliphatic in nature are. However, the preparation of the catalysts is complex and technically not harmless due to the toxicity of organic phosphines, phosphine oxides, phosphoric acid derivatives, etc. (US Pat. No. 3,911 Q41).

Weiterhin wurde versucht, die Bildung alkylierter Aromaten durch Einstellung bestimmter verfahrenstechnischer Parameter, z.B. Herabsetzung des Partialdruckes des Einsatz-Methanols, zu verhindern. Wie beispielsweise aus der US-PS 4 025 575 hervorgeht, läßt sich durch Verdünnung des als Einsatz dienenden Methanols mit inerten Gasen die Aromatenbildung unterdrücken und die niederen Olefinen, erhöhen. Es ist offenkundig, daß eine solche Verfahrensweise mit technischen Problemen hinsichtlich Raum-Zeit-Ausbeute, Gasrückführung und Trennung der Reaktionsprodukte von den gasförmigen Inertstoffen belastet ist.Attempts have also been made to prevent the formation of alkylated aromatics by setting certain process parameters, e.g. To prevent the partial pressure of the feed methanol from being reduced. As can be seen, for example, from US Pat. No. 4,025,575, dilution of the methanol used as an insert with inert gases can suppress the formation of aromatics and increase the lower olefins. It is evident that such a procedure is burdened with technical problems with regard to space-time yield, gas recirculation and separation of the reaction products from the gaseous inert substances.

überraschenderweise wurde nun gefunden, daß die katalytische Umwandlung von Methanol und/oder Dimethylether in Gegenwart des Zeolithen PSH-3 ein Kohlenwasserstoffgemisch liefert, daß einen niedrigen Aromatengehalt aufweist.Surprisingly, it has now been found that the catalytic conversion of methanol and / or dimethyl ether in the presence of the zeolite PSH-3 provides a hydrocarbon mixture which has a low aromatic content.

Die erfindungsgemäße Anwendung des Zeoliths PSH-3 als Katalysator, zur Umwandlung von Methanol und/oder Dimethylether kann entweder diskontinuierlich, halbkontinuierlich oder kontinuierlich durchgeführt werden. Dabei ist es unerheblich, ob der Katalysator fest oder beweglich angeordnet ist.The inventive use of the zeolite PSH-3 as a catalyst for the conversion of methanol and / or dimethyl ether can be carried out either batchwise, semi-continuously or continuously. It is irrelevant whether the catalyst is fixed or movable.

Die nachfolgende Erläuterung bezieht sich auf Methanol als Einsatzmaterial. Es ist jedoch zu berücksichtigen, daß mit gleichem Erfolg aus Dimethylether oder Dimethylether-Wasser-Mischungen eingesetzt werden können.The following explanation refers to methanol as the feed. However, it must be taken into account that dimethyl ether or dimethyl ether / water mixtures can be used with equal success.

Der Methanol-Einsatz kann aus reinem Methanol oder aus Wasser- und oxygenathaltigem technichem Rohmethanol bestehen. Ebenso kann eine zusätzliche Verdünnung des Einsatzes mit Wasser vorgenommen werden.The methanol insert can consist of pure methanol or of technical crude methanol containing water and oxygenate. An additional dilution of the insert with water can also be carried out.

Das Verfahren ist durch folgende Raktionsbedingungen gekennzeichnet:

Figure imgb0011
The process is characterized by the following conditions:
Figure imgb0011

Es kann notwendig sein, den verwendeten Katalysator auf Basis Zeolith PSH-3 nach einer gewissen Betiebsdauer von desaktivierenden Ablagerungen zu befreien. Diese Regenerierung wird zweckmäßigerweise durch .Zufuhr einer sauerstoffhaltigen Atmosphäre, (z.B. Luft oder Luft-Stickstoff-Gemische) zum Katalysator bei erhöhter Temperatur nach bekannten Techniken durchgeführt. Die Regeneriertemperatur sollte 600°C nicht übersteigen.It may be necessary to remove the deactivating deposits from the zeolite-based PSH-3 catalyst after a certain operating time. This regeneration is expediently carried out by supplying an oxygen-containing atmosphere (for example air or air-nitrogen mixtures) to the catalyst at elevated temperature using known techniques. The regeneration temperature should not exceed 600 ° C.

Ebenso kann anstelle von Methanol und/oder Dimethylether direkt Synthesegas als umzuwandelndes Einsatzmaterial verwendet werden, sofern der Zeolith PSH-3 mit für die Methanol- bzw. Fischer-Tropsch-Synthese katalytisch geeigneten Metallen belegt ist.Similarly, instead of methanol and / or dimethyl ether, synthesis gas can be used directly as the feedstock to be converted, provided that the zeolite PSH-3 is coated with metals which are catalytically suitable for the methanol or Fischer-Tropsch synthesis.

Das erfindungsgemäße Alumosilicat kann so in Verbindung mit Katalysatoren eingesetzt werden, die für die Kohlenoxidhydrierung geeignet sind. Während die bei der üblichen-Ausführung der.Kohlenoxidhydrierung (FISCHER- TROPSCH-Synthese mit metallhaltigen Katalysatoren) entstehende Fraktion der längerkettigen Kohlenwasserstoffe (C5+) oft bis über 20 bis 25 C-Atome im Molekül aufzeigt und zum großen Teil geradkettig aufgebaut ist, liefert die Anwendung des erfindungsgemäßen Alumosilicats als Cokatalysator bei der katalytischen Kohlenoxidhydrierung neben anderen Produktbestandteilen ein Ce-Kohlenwasserstoffgemisch, das überwiegend aus Molekülen mit 5 bis 12 C-Atomen besteht. Dieser kettenlängenbegrenzende Effekt des erfindungsgemäßen Alumosilicats ist bei entsprechender Führung der Reaktion mit einer Bildung verzweigter Kohlenwasserstoffe und gegebenenfalls weiteren, zu Aromaten führenden Reaktionen verbunden, wodurch z.B. ein so hergestellte Kohlenwasserstoffgemisch zur Weiterverarbeitung in Ottokraftstoff wesentlich besser geeignet ist als das bei der üblichen Ausführung der FISCHER-TROPSCH-Synthese entstehende Kohlenwasserstoffgemisch.The aluminosilicate according to the invention can thus be used in conjunction with catalysts which are suitable for the hydrogenation of carbon oxides. While the fraction of longer-chain hydrocarbons (C 5+ ) that occurs in the usual implementation of the carbon oxide hydrogenation (FISCHER- T ROPSCH synthesis with metal-containing catalysts) often shows up to over 20 to 25 C atoms in the molecule and is largely straight-chain , the application of the aluminosilicate according to the invention as a cocatalyst in the catalytic hydrogenation of carbon dioxide provides, among other product components, a Ce-hydrocarbon mixture which consists predominantly of molecules with 5 to 12 carbon atoms. This chain length-limiting effect of the aluminosilicate according to the invention is associated with the formation of branched hydrocarbons and possibly further reactions leading to aromatics if the reaction is carried out appropriately, so that, for example, a hydrocarbon mixture prepared in this way is much more suitable for further processing in petrol than is the case with the usual execution of FISCHER TROPSCH synthesis resulting hydrocarbon mixture.

Anhand der folgenden Beispiele soll die Erfindung noch häher erläutert werden. %-Angaben beziehen sich - soweit nicht anders vermerkt ist - auf Gew.-%.The following examples are intended to explain the invention in greater detail. Unless otherwise stated,% figures relate to% by weight.

Beispiel 1example 1

In einem 2 Liter Stahl-Autoklay mit Rühreinsatz wird eine Mischung aus 217 ml Wasserglas (27 % SiO2 und 8 % Na2O) und 316 ml Wasser mit 49,5 g Hexamethylenimin versetzt und intensiv gerührt. In diese Mischung läßt man langsam unter Rühren eine Lösung aus 9,22 g Al-Sulfat, 23,4 g H2SO4 (konz.) und 460 ml Wasser einfließenA mixture of 217 ml water glass (27% SiO 2 and 8% Na 2 O) and 316 ml water is mixed with 49.5 g hexamethyleneimine and stirred vigorously in a 2 liter steel autoclave with a stirring insert. A solution of 9.22 g of Al sulfate, 23.4 g of H 2 SO 4 (conc.) And 460 ml of water is slowly poured into this mixture with stirring

Nachdem das entstandene Reaktionsgel homogenisiert worden ist, läßt man bei 150°C innerhalb von 70 Stunden kristallisieren.After the resulting reaction gel has been homogenized, it is left to crystallize at 150 ° C. within 70 hours.

Nach Ende der Reaktionszeit wird der Feststoff von der flüssigen Phase abgetrennt, ausgewaschen, bis der pH-Wert bei 7-9 lag und bei 120°C getrocknet.At the end of the reaction time, the solid is separated from the liquid phase, washed out until the pH was 7-9 and dried at 120.degree.

Der Zeolith hatte die in der Tabelle angegebenen Röntgenbeugungsdaten und nach dem Calcinieren bei 500°C fol .gende Zusammensetzung: 0,4 Na2O · Al2O3 · 55 SiO2.

Figure imgb0012
Figure imgb0013
The zeolite had the specified table in the X-ray diffraction data and after calcination at 500 ° C fol. The following composition: 0.4 Na 2 O.Al 2 O 3 .55 SiO 2 .
Figure imgb0012
Figure imgb0013

Beispiel 2Example 2

100 g Zeolith PSH-3 in der calcinierten Form werden mit 1000 ml 0,5 n HCl bei 80°C 5 Stunden gerührt. Der Feststoff wird abgetrennt und gewaschen. Der Austausch wird noch zweimal wiederholt. Die H-Form des Zeoliths kann als Katalysator für die Herstellung von Kohlenwasserstoffen aus Methanol eingesetzt werden.100 g of zeolite PSH-3 in the calcined form are stirred with 1000 ml of 0.5N HCl at 80 ° C. for 5 hours. The solid is separated off and washed. The exchange is repeated two more times. The H form of the zeolite can be used as a catalyst for the production of hydrocarbons from methanol.

Beispiel 3Example 3

Der Ansatz wie in Beispiel 1 wurde.bei 130°C innerhalb von 144 Stunden kristallisiert. Das erhaltene kristalline Produkt wies die identischen Röntgendaten wie der Zeolith PSH-3 aus Beispiel 1 auf.The batch as in Example 1 was crystallized at 130 ° C. within 144 hours. The crystalline product obtained had the same X-ray data as the zeolite PSH-3 from Example 1.

Beispiel 4Example 4

In einem 5 Liter Stahl-Autoklav mit Rührereinsatz wird eine Mischung aus 650 g Kieselsol, 790 ml Wasser und 78 g NaOH mit 124 g Hexamethylenimin versetzt. diese Mischung wird langsam eine Lösung aus. 23 g Al-Sul- fat, 58,5 g H2SO4 (konz.) und 1150 ml H20 gegegeben.A mixture of 650 g of silica sol, 790 ml of water and 78 g of NaOH is mixed with 124 g of hexamethyleneimine in a 5 liter steel autoclave with a stirrer insert. this mixture slowly becomes a solution. 23 g of Al-sulfonic fa t, 58.5 g H 2 SO 4 (conc.) And 1150 ml H 2 0 woks.

Das Reaktionsgemisch läßt man bei 150°C 5 Tage unter Rühren kristallisieren.The reaction mixture is allowed to crystallize at 150 ° C. for 5 days with stirring.

Der kristalline Feststoff wird abgetrennt, ausgewaschen, bis der pH-Wert im ablaufenden Wasser 8-9 betrug. Der Zeolith hatte nach dem Calcinieren die Röntgenbeugungsdaten der Tabelle 1.The crystalline solid is separated off, washed out until the pH in the effluent water was 8-9. After calcination, the zeolite had the X-ray diffraction data in Table 1.

Beispiel 5Example 5

Ansatz wie in Beispiel 1, nur wurde hier die Menge des Hexamethylenimins um 50 % reduziert. Die Kristallisation erfolgte bei 140°C innerhalb von 96 Stunden.Approach as in Example 1, except that the amount of hexamethyleneimine was reduced by 50%. The crystallization took place at 140 ° C. within 96 hours.

Das kristalline Endprodukt wies hauptsächlich die Röntgendaten der Tabelle 1 auf, neben geringen Mengen an Quarz.The crystalline end product mainly had the X-ray data in Table 1, in addition to small amounts of quartz.

Beispiel 6Example 6

Ansatz wie in Beispiel 1, nur wurde hier die Menge des Al-Sulfats auf 15 g erhöht. Das kristalline Endprodukt wies nach der Calcinierung folgende oxidische Zusammensetzung auf: 0,2 Na20, A1203, 41 Si02.Approach as in Example 1, except that the amount of Al sulfate was increased to 15 g. After the calcination, the crystalline end product had the following oxidic composition: 0.2 Na 2 0, A1 2 0 3 , 41 Si0 2 .

Die Röntgendaten stimmten im wesentlichen mit denen der Tabelle 1 überein.The X-ray data were essentially the same as those in Table 1.

Die nachfolgenden Beispiele 7 bis 8 betreffen die Verwendung des nach den Beispielen 1-6 hergestellten Zeoliths PSH-3 als Katalysator für die Umwandlung von Methanol und/oder Dimethylether in Kohlenwasserstoffe.Examples 7 to 8 below relate to the use of the zeolite PSH-3 prepared according to Examples 1-6 as a catalyst for the conversion of methanol and / or dimethyl ether into hydrocarbons.

Beispiel 7Example 7

Ein nach Beispiel 1 hergestellter und nach Beispiel 2, dekationisierter Zeolith PSH-3 wurde mit 15 % Bentonit versetzt und mit Wasser zu einer extrudierbaren Masse verarbeitet. Nach Extrusion, Trocknung bei 120°C und Calcinierung bei 500°C wurden Katalsator-Formkörper erhalten. Die Ausprüfung dieses Katalysatormaterials erfolgte ohne Anwendung von Druck in einem elektrisch beheiztem Rohrreaktor (d = 20 mm, Katalysator-Füllhöhe 160 mm), der mit einer Vorheizzone sowie Einlässen für Stickstoff und Methanol versehen war.A zeolite PSH-3 prepared according to Example 1 and decationized according to Example 2 was mixed with 15% bentonite and processed with water to an extrudable mass. After extrusion, drying at 120 ° C. and calcination at 500 ° C., shaped catalyst bodies were obtained. This catalyst material was tested without applying pressure in an electrically heated tubular reactor (d = 20 mm, catalyst filling height 160 mm), which was provided with a preheating zone and inlets for nitrogen and methanol.

Der Katalysator wurde unter Stickstoff auf eine Reaktionstemperatur von 370°C gebracht und dann mit gasförmigem Methanol in einer Menge von 790 g pro Liter Katalysator und Stunde beaufschlagt.The catalyst was brought to a reaction temperature of 370 ° C. under nitrogen and then charged with gaseous methanol in an amount of 790 g per liter of catalyst per hour.

Der Methanolumsatz betrug bei diesem Versuch 94,5 Gew.-%. Neben Wasser und nichtumgesetztem Methanol wurde ein organisches Reaktionsprodukt der folgenden Zusammensetzung erhalten (Angaben in Gewichtsprozent):

Figure imgb0014
The methanol conversion in this experiment was 94.5% by weight. In addition to water and unreacted methanol, an organic reaction product of the following composition was obtained (percentages by weight):
Figure imgb0014

Da der bei der Reaktion entstehende Dimethylether rezirkulierbar ist, errechnet sich für die Summe der C

Figure imgb0015
- Kohlenwasserstoffe eine Kohlenstoff-Selektivität von ca. 46 %. Unter Einbeziehung der C
Figure imgb0016
-Kohlenwassarstoffe erhöht sich dieser Wert auf ca. 84 %. Hierdurch wird offenbar, daß sich Zeolith PSH-3 in besonderer Weise für die Herstellung eines olefinreichen, aliphatischen Kohlenwasserstoffgemisches aus Methanol eignet.Since the dimethyl ether formed during the reaction can be recirculated, the sum of the C
Figure imgb0015
- Hydrocarbons have a carbon selectivity of approx. 46%. Including the C
Figure imgb0016
- Hydrocarbons this value increases to approx. 84%. This shows that zeolite PSH-3 is particularly suitable for the production of an olefin-rich, aliphatic hydrocarbon mixture from methanol.

Beispiel 8Example 8

Dieses Beispiel bezieht sich auf die Umwandlung einer Methanol/Dimethylether/Wasser-Gleichgewichtsmis-hung in überwiegend aliphatisch-olefinische Kohlenwasserstoffe. Ein Strom von 50 ml Methanol pro Stunde wurde in ver- dampfter Form ohne Anwendung von Druck bei einer Temperatur von 280°C über eine Katalysatorschüttung bestehend aus 100 ml gefälltem und granuliertem Aluminiumoxid geleitet. Aus der Literatur ist bekannt, daß Aluminiumoxid die Umsetzung von Methanol zu Dimethylether katalysiert (siehe beispielsweise J.B. Senderens, Ann. Chim. Phys. 25, 509 (1912). Das den Reaktor verlassende Produktgemisch wurde ohne weitere Trennung über einen nach Beispiel 1 und 2 hergestellten und mit einem Zusatz von 20 % Montigel nach bekannten Techniken granulierten Katalysator auf Basis Zeolith PSH-3 geleitet.This example relates to the conversion of a methanol / dimethyl ether / water equilibrium mixture into predominantly aliphatic-olefinic hydrocarbons. A stream of 50 ml of methanol per hour was passed in vaporized form without applying pressure at a temperature of 280 ° C. over a bed of catalyst consisting of 100 ml of precipitated and granulated aluminum oxide. It is known from the literature that aluminum oxide catalyzes the conversion of methanol to dimethyl ether (see, for example, JB Senderens, Ann. Chim. Phys. 25, 509 (1912). The product mixture leaving the reactor was passed through a mixture according to Examples 1 and 2 without further separation prepared and granulated with an addition of 20% Montigel according to known techniques based on zeolite PSH-3.

Die Kontaktbelastung betrug 800 g Einsatz pro Liter Katalysator und Stunde; die Umwandlungstemperatur betrug 370°C.The contact load was 800 g insert per liter catalyst and hour; the transition temperature was 370 ° C.

Der den Reaktor verlassende Produktstrom setzte sich wie folgt zusammen (ohne Berücksichtigung des Reaktionswassers):

Figure imgb0017
The product stream leaving the reactor was composed as follows (without taking the water of reaction into account):
Figure imgb0017

Im C

Figure imgb0018
-Anteil können auch kleine Anteile sauerstoffhaltiger Verbindungen enthalten sein.
Figure imgb0019
Da der entstandene Dimethylether zurückgeführt werden kann, errechnet sich für die aliphatischen Kohlenwasserstoffe im Benzinsiedebereich (C
Figure imgb0020
, P + O) eine Kohlenstoff-Selektivität von ca. 47 %. Dieser Wert erhöht sich auf ca. 83 %, sofern auch C3-'und C4-Kohlenwasserstoffe hinzugenommen werden. Aus Letzteren lassen sich nach bekannten Techniken (Alkylierungsprozesse) ebenfalls Vergaserkraftstoffe gewinnen.In the C
Figure imgb0018
-Share can also contain small amounts of oxygen-containing compounds.
Figure imgb0019
D can be a the resultant dimethyl ether recycled, is calculated for the aliphatic hydrocarbons in the B enzinsiedebereich (C
Figure imgb0020
, P + O) a carbon selectivity of approx. 47%. This value increases to approx. 83% if C 3 and C 4 hydrocarbons are also added. Carburetor fuels can also be obtained from the latter using known techniques (alkylation processes).

Beispiel 9Example 9

Zur Herstellung eines Katalysators zur Kohlenoxidhydrierung wurde eine Suspension aus 18,4 g des erfindungsgemäßen Alumosilicats in 250 ml einer wäßrigen Lösung mit 18,4 g Kaliwasserglas und 70,1 g Fe(N03)3 x 9 H20 in der Siedehitze mit 160 ml 11 %-iger Ammoniaklösung versetzt. Der Niederschlag wurde abfiltriert, mit Wasser neutral gewaschen und 4 h bei 150°C im Vakuum (20 Torr) getrocknet. Nach Mahlung wurde die Masse mit Graphit und Bentonit zu zylindrischen 5 x 5 mm-Tabletten gepreßt. Unter der Annahme vollständiger Ausfällung des Eisens und quantitativer Sorption des Kaliwasserglases durch den Niederschlag berechnet man folgende Katalysatorzusammensetzung:

Figure imgb0021
50 ml dieses das erfindungsgemäße Alumosilicat enthaltenden Kohlenoxidhydrierungskatalysators wurden zur besseren Wärmeabfuht mit 450 ml eines überwiegend aus Siliciumcarbid bestehenden Materials (Norton SC 5232) vermischt und in einen mit Wärmeträgeröl thermostatisierten Rohrreaktor von 25 mm Durchmesser und 150 cm Länge ge7 füllt. Die Katalysatorfüllung wurde zunächst 14 h lang bei 300°C, Normaldruck und einer Gasbelastung von 1000 Nl/(h x 1 Katalysator) sowie anschließend mit Kohlenmonoxid 8 h lang bei 300°C, Normaldruck und einer Gasbelastung von-1000 Nl/(h x 1 Katalysator) behandelt. Die hier und in der folgenden, die Ergebnisse der Kohlenoxidhydrierung enthaltenden Tabelle angegebenen Gasbelastungen beziehen sich stets auf die eingesetzten 50 ml des oben beschriebenen Katalysators. Die kettenlängenbegrenzende Wirkung des erfindungsgemäßen Alumosilicats geht aus den Angaben der beiden Beispiele hervor, wonach 95 Gew.% der C5+-Fraktion ≤ 12 C-Atome im Molekül aufweisen.
Figure imgb0022
Figure imgb0023
To prepare a catalyst for hydrogenation of carbon oxides, a suspension of 18.4 g of the aluminosilicate according to the invention in 250 ml of an aqueous solution with 18.4 g of potassium water glass and 70.1 g of Fe (N0 3 ) 3 × 9 H 2 0 was boiled at 160 ml of 11% ammonia solution are added. The precipitate was filtered off, washed neutral with water and dried for 4 h at 150 ° C. in vacuo (20 torr). After grinding, the mass was pressed with graphite and bentonite into cylindrical 5 x 5 mm tablets. Assuming complete precipitation of the iron and quantitative sorption of the potash water glass by the precipitation, the following catalyst composition is calculated:
Figure imgb0021
50 ml of this aluminosilicate containing Kohlenoxidhydrierungskatalysators according to the invention were better for Wärmeabfuht with 450 ml of a predominantly consisting of silicon carbide material (Norton SC 5232) were mixed and ge in a thermostated heat-transfer oil tubular reactor of 25 mm in diameter and 150 cm in length filled. 7 The catalyst was first filled for 14 h at 300 ° C, normal pressure and a gas load of 1000 Nl / (hx 1 catalyst) and then with carbon monoxide for 8 h at 300 ° C, normal pressure and a gas load of-1000 Nl / (hx 1 catalyst ) treated. The gas loads indicated here and in the following, which contain the results of the carbon oxide hydrogenation, always relate to the 50 ml of the catalyst described above. The chain length-limiting effect of the aluminosilicate according to the invention can be seen from the information in the two examples, according to which 95% by weight of the C 5+ fraction has 12 12 C atoms in the molecule.
Figure imgb0022
Figure imgb0023

Claims (9)

1. Kristallines Alumosilicat mit einer Zusammensetzung entsprechend der Formel (in Molverhältnissen der Oxide):
Figure imgb0024
wobei M ein Kation der Wertigkeit n ist und mit einem Pulver-Röntgendiagramm im wesentlichen wie in Tabelle 1 angegeben.
1. Crystalline aluminosilicate with a composition according to the formula (in molar ratios of the oxides):
Figure imgb0024
where M is a cation of valence n and with a powder X-ray diagram essentially as indicated in Table 1.
2. Verfahren zur Herstellung von kristallinem Alumosilicat nach Anspruch 1, dadurch gekennzeichnet, daß die Synthese in Gegenwart von Hexamethylenimin erfolgt.2. A process for the preparation of crystalline aluminosilicate according to claim 1, characterized in that the synthesis takes place in the presence of hexamethyleneimine. 3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß die Synthese in folgendem Bereich der oxidischen Molverhältnisse erfolgt:
Figure imgb0025
(R = Hexamethylenimin)
3. The method according to claim 2, characterized in that the synthesis takes place in the following range of the oxidic molar ratios:
Figure imgb0025
(R = hexamethyleneimine)
4. Verwendung von kristallinem Alumosilicat gemäß Anspruch 1 als Katalysator für die katalytische Umwandlung von Methanol und/oder Dimethylether in Kohlenwasserstoffe.4. Use of crystalline aluminosilicate according to claim 1 as a catalyst for the catalytic conversion of methanol and / or dimethyl ether into hydrocarbons. 5.- Verwendung gemäß Anspruch 4, dadurch gekennzeichnet, daß das kristalline Alumosilicat in ionenausgetauschter Form zum Einsatz gelangt.5.- Use according to claim 4, characterized in that the crystalline aluminosilicate is used in ion-exchanged form. 6. Verwendung gemäß Anspruch 4, dadurch gekennzeichnet, daß das kristalline Alumosilicat in der H-Form eingesetzt wird.6. Use according to claim 4, characterized in that the crystalline aluminosilicate is used in the H form. 7. Verwendung gemäß Anspruch 4, dadurch gekennzeichnet, daß das kristalline Alumosilicat in einer Metall.-ausgetauschten Form zum Einsatz gelangt.7. Use according to claim 4, characterized in that the crystalline aluminosilicate is used in a metal-exchanged form. 8. Verwendung von kristallinen Alumosilicat gemäß Anspruch 1 in Verbindung mit anderen Katalysatoren für die Kohlenoxidhydrierung.8. Use of crystalline aluminosilicate according to claim 1 in conjunction with other catalysts for carbon oxide hydrogenation. 9. Verwendung von kristallinen Alumosilicats gemäß Anspruch 1 in ionenausgetauschter Form und in Verbindung mit Katalysatoren für die Kohlenoxidhydrierung.9. Use of crystalline aluminosilicate according to claim 1 in ion-exchanged form and in connection with catalysts for the carbon oxide hydrogenation.
EP82103256A 1981-04-30 1982-04-19 Crystalline aluminosilicate, process for producing it and its use in converting methanol and/or dimethyl ether into hydrocarbons Expired EP0064205B1 (en)

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